Platinum is a Photocatalyst: Large Visible-Light Quantum Efficiency Revealed

Metal-semiconductor junctions in optoelectronic devices are commonly engineered to promote charge separation. In Pt/TiO2 Schottky junctions, Pt is typically regarded as a catalytic electron sink rather than a visible-light-active component. Here, we demonstrate that Pt nanoislands on TiO2 can generate photochemically active carriers under visible light excitation. Using quantitative scanning photoelectrochemical microscopy, we measure the wavelength-resolved external quantum efficiency (EQE) of Au and Pt nanoisland arrays on TiO2, and correlate their reactivity with their morphology and extinction spectra. Discrete 10 nm Pt nanoislands exhibit robust broadband visible light photoactivity - exceeding the photoactivity of similar-sized Au nanoislands under blue-green excitation - whereas Pt's photoactivity is strongly suppressed when the nanoislands are connected. Surprisingly, Pt exhibits an EQE-per-atom approx. 20 times higher than Au at 455 nm and approx. 2 times higher at 595 nm (at Au's optimum). We show an approximately wavelength-independent Pt internal quantum efficiency of approx. 1 percent across the visible spectral region. These findings reposition catalytic metals with strongly damped optical response in the visible as light-responsive components in metal-semiconductor hybrids, challenging the prevailing perception that they function solely as passive co-catalysts in photocatalytic systems.